CN108311057B - Nonionic surfactant with comb-shaped structure and preparation method thereof - Google Patents

Nonionic surfactant with comb-shaped structure and preparation method thereof Download PDF

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CN108311057B
CN108311057B CN201810050225.6A CN201810050225A CN108311057B CN 108311057 B CN108311057 B CN 108311057B CN 201810050225 A CN201810050225 A CN 201810050225A CN 108311057 B CN108311057 B CN 108311057B
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phenol
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pentadecenyl
comb
catalyst
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顾斌
戴志成
孙怡洁
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CHANGSHU NAISU BIOLOGICAL MATERIAL TECHNOLOGY CO LTD
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups

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Abstract

The invention discloses a nonionic surfactant with a comb-type structure, which is alkaneAn oxyalkylated oligomeric pentadecenyl meta-phenol comprising at least one member of the formula:

Description

Nonionic surfactant with comb-shaped structure and preparation method thereof
Technical Field
The invention relates to the field of surfactants, in particular to a nonionic surfactant with a comb-shaped structure and a preparation method thereof.
Background
The high molecular surfactant is a polymer having a surface activity of at least thousands relative to the molecular mass of the low molecular surfactant. The most used polymeric surfactants are natural water-soluble polymers such as natural sodium alginate, various starches, celluloses and derivatives thereof, which are used as colloid protective agents and auxiliary agents, and although they have certain emulsifying and dispersing abilities, the surface activity of the polymers is low because the polymers have more hydrophilic groups. In 1951, Strass named poly (1-dodecyl-4-vinylpyridine bromide) to which surface active functional groups were bonded as polysoap, and synthetic polymeric surfactants were developed. In 1954, Wyandotte company in the United states reported that a nonionic polymer surfactant, i.e., a block copolymer of polyoxyethylene and polyoxypropylene, and various synthetic polymer surfactants with high performance were developed in succession and widely used in various fields. Compared with low molecular surfactant, the high molecular surfactant has the advantages of high solution viscosity and good film forming property, is a polymer material with great application prospect in oil exploitation and paint industry, has wide application in bionic film, and has become the object of intercross research of chemistry, chemical engineering, petroleum, materials, life science and the like at present.
In recent years, from the viewpoint of molecular design, some polymer surfactants having specific structures (comb type, star type, etc.) have been synthesized to enhance the ability of alignment at the interface. Therefore, the polymer surfactant integrating emulsification and thickening is expected to be prepared. The novel amphoteric high-molecular surfactant with anions and non-ions is prepared by copolymerizing maleic anhydride and styrene and then reacting with peregal, and the stabilizing effect of the surfactant on paraffin hydrocarbon emulsion is investigated. The results show that the novel macromolecular surfactant has better thickening and stabilizing effects on the emulsion than the similar polycarboxylic acid anionic macromolecular surfactant and peregal nonionic surfactant which are compounded. Although many common surfactants have a dispersing effect, the dispersing effect of the common surfactants is often very limited and the dosage is large due to the influence of factors such as molecular structures, relative molecular masses and the like. The macromolecular surfactant has adjustable hydrophilic group, hydrophobic group, position and size, comb-shaped molecular structure and multi-branched structure, so that it has stronger surface covering and encapsulating effect on dispersed particles than the former. The dispersion system of the dispersant is more stable and fluid, so the dispersant is a promising dispersant.
Disclosure of Invention
The invention mainly solves the technical problem of providing a nonionic surfactant with a comb-shaped structure and a preparation method thereof.
In order to solve the technical problems, the invention adopts a technical scheme that: providing a nonionic surfactant with a comb structure, wherein the nonionic surfactant with the comb structure is alkoxylated oligomeric pentadecenyl (alkyl) meta-phenol and comprises at least one component with the following structural formula:
Figure BDA0001552144810000021
wherein,
Figure BDA0001552144810000022
natural cardanol or hydrogenated cardanol;
the M is a micromolecule connecting group which is connected to the ortho-position or para-position of the phenolic hydroxyl;
p, Q is one or more alkoxy groups which may be the same or different;
x is an integer and is more than or equal to 0 and less than or equal to 30;
m is an integer or a fraction, and m is more than or equal to 0 and less than or equal to 100;
n is an integer or a fraction, and n is more than or equal to 1 and less than or equal to 100.
In a preferred embodiment of the present invention, R is1is-C15H25、-C15H27、-C15H29Or C15H31Linear (poly) ene (alk) hydrocarbon structures of (i).
In a preferred embodiment of the invention, the alkoxy group is-CH2CH2O-、-CH2CH(CH3) O-or-CH2CH(CH2CH3)O-。
In a preferred embodiment of the present invention, M is-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(OH)-CH(OH)-、-CH(OH)-CH2-CH(OH)-、-CH(OH)-CH2-CH2-CH2-CH(OH)-、-CH2-NH-CH2-、-CH2-N(CH3)-CH2-、-CH2-N(CH2CH3)-CH2-、-CH2-N(CH2CH2CH3)-CH2-、-CH2-N(CH2CH2OH)-CH2-、-CH2-N(CH3)-N(CH3)-CH2-or-CH2-NH-CH2-CH2-NH-CH2--CH2-NH-CH2-。
In order to solve the technical problem, the invention adopts another technical scheme that: provides a preparation method of a nonionic surfactant with a comb-type structure, which comprises the following steps:
(1) synthesis of pentadecenyl meta-phenol oligomers: adding (x +2) mol of refined pentadecenyl m-phenol and a catalyst I into a reactor, adding (x +1) mol of a connecting agent in batches at 50-80 ℃, and carrying out reflux reaction in a nitrogen atmosphere to remove small molecular substances to obtain a pentadecenyl (alkyl) m-phenol polymer;
(2) synthesis of alkoxylated oligo pentadecenyl meta-phenol: adding the oligomer obtained in the step (1) and a catalyst II into a high-pressure reactor, replacing with nitrogen, removing small molecular substances, and then sequentially adding (x +2) m moles of an alkoxylation reagent and (x +2) n moles of an alkoxylation reagent to perform two-stage alkoxylation reaction; and finally, preserving heat and curing until the pressure is constant, and adjusting the pH value of the system to be 5-8 to obtain the alkoxylated oligomeric pentadecenyl m-phenol.
In a preferred embodiment of the invention, in the step (1), the addition amount of the catalyst I is 0.2-2.0% of the addition amount of the pentadecenyl m-phenol; the technological conditions of the reflux reaction are as follows: the temperature is increased to 80-100 ℃ for reflux reaction for 1-3 h, and then the temperature is increased to 100-180 ℃ for reflux reaction for 1-3 h.
In a preferred embodiment of the invention, in the step (2), the addition amount of the catalyst II accounts for 0.03-1.0% of the addition mass of the polymer; the two-stage alkoxylation reaction conditions are as follows: the temperature is 100-200 ℃, the pressure is below 0.45MPa, and the adding speed of the alkoxylating reagent is used for keeping the reaction pressure not more than 0.45 MPa.
In a preferred embodiment of the invention, in the step (2), the temperature for the heat preservation and curing is 120-180 ℃ for 0.5-4 h; the pH value regulator is weak acid or weak base.
In a preferred embodiment of the invention, the catalyst I is one or a mixture of more than two of acidic or basic compounds; wherein, the acidic compound comprises various inorganic acids, organic acids or other strong acid weak base salt compounds with obvious acidity; the alkaline compound comprises inorganic base, organic base or other strong base weak acid salt compound which shows alkalinity; the catalyst II is one or a mixture of more than two of an alkaline catalyst, an acidic catalyst or a double metal cyanide complex; the alkoxylating agent includes ethylene oxide, propylene oxide or butylene oxide.
In a preferred embodiment of the present invention, the inorganic acid includes hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; organic acids include formic acid, oxalic acid, citric acid, tartaric acid, lactic acid, p-methanesulfonic acid or alkylbenzenesulfonic acid; the inorganic base comprises potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide, magnesium hydroxide or calcium hydroxide; the organic base comprises sodium methoxide, sodium ethoxide, sodium lauryl oxide or sodium isopropoxide; in the catalyst II, the basic catalyst comprises alkali metal in the I main group or alkaline earth metal in the II main group, alkali metal or alkaline earth metal alkoxide, oxide or hydroxide and strong alkali weak acid salt showing alkalinity; the acidic catalyst comprises a protic or lewis acid.
The invention has the beneficial effects that: the preparation process of the nonionic surfactant with the comb-shaped structure has the advantages of short flow, strong operability, high solid content of the prepared surfactant product, moderate viscosity, integration of emulsification and thickening performance, stable apparent performance, adjustable molecular weight, comb-shaped molecular structure, multi-branched structure, good covering and encapsulating effects on the surface of dispersed particles, and wide application prospect in the industrial fields of aqueous color paste dispersion, emulsification of pesticide raw materials, papermaking, textile printing and dyeing, wastewater treatment, crude oil exploitation and the like.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and unequivocally define the scope of the present invention.
The embodiment of the invention comprises the following steps:
the invention discloses a nonionic surfactant with a comb-type structure, which is alkoxylated oligomeric pentadecenyl meta-phenol and comprises at least one component with the following structural formula:
Figure BDA0001552144810000051
wherein,
Figure BDA0001552144810000052
is natural cardanol or hydrogenated cardanol with different hydrogenation degree, R in the formula1is-C15H25、-C15H27、-C15H29Or C15H31Linear (poly) ene (alk) hydrocarbon structures of (i).
M is a micromolecular connecting group which is connected at the ortho-position or the para-position of the phenolic hydroxyl and is-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(OH)-CH(OH)-、-CH(OH)-CH2-CH(OH)-、-CH(OH)-CH2-CH2-CH2-CH(OH)-、-CH2-NH-CH2-、-CH2-N(CH3)-CH2-、-CH2-N(CH2CH3)-CH2-、-CH2-N(CH2CH2CH3)-CH2-、-CH2-N(CH2CH2OH)-CH2-、-CH2-N(CH3)-N(CH3)-CH2-or-CH2-NH-CH2-CH2-NH-CH2--CH2-NH-CH2-。
P, Q is one or more same or different alkoxy, specifically, P is-CH2CH2O-、-CH2CH(CH3) O-or-CH2CH(CH2CH3) One or a combination of more than one of O-; q is-CH2CH2O-、-CH2CH(CH3) O-or-CH2CH(CH2CH3) O-, or a combination of more than one kind.
X is an integer and is more than or equal to 0 and less than or equal to 30;
m is an integer or a fraction, and m is more than or equal to 0 and less than or equal to 100;
n is an integer or a fraction, and n is more than or equal to 1 and less than or equal to 100.
The preparation method of the nonionic surfactant with the comb-type structure specifically comprises the following steps:
(1) synthesis of pentadecenyl meta-phenol oligomers: putting (x +2) moles of refined pentadecene (alkyl) group m-phenol into a reactor, adding a catalyst I accounting for 0.2-2.0% of the added weight of the pentadecene (alkyl) group m-phenol, heating to 50-80 ℃, adding (x +1) moles of small molecule linking agent in batches, then heating to 80-100 ℃ in a nitrogen atmosphere for reflux reaction for 1-3 h, heating to 100-180 ℃ for reflux reaction for 1-3 h, then vacuumizing to remove water or hydrogen halide and other small molecules for polycondensation reaction, and obtaining a pentadecene (alkyl) group m-phenol polymer;
wherein, the catalyst I is one or a mixture of more than two of acidic or basic compounds.
The acidic compound includes various inorganic acids, organic acids or other strong acid weak base salt compounds which show acidity. Wherein the inorganic acid comprises hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.; the organic acid includes formic acid, oxalic acid, citric acid, tartaric acid, lactic acid, p-methanesulfonic acid, alkylbenzenesulfonic acid, etc.
The alkaline compound comprises inorganic base, organic base or other strong base weak acid salt compounds which show alkalinity. Wherein the inorganic base comprises potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide, magnesium hydroxide, calcium hydroxide and the like; the organic base includes sodium methoxide, sodium ethoxide, sodium laurylate, sodium isopropoxide, etc.
(2) Synthesis of alkoxylated oligo pentadecenyl meta-phenol: adding the pentadecenyl (alkyl) m-phenol oligomer obtained in the step (1) into a high-pressure reactor, adding a catalyst II under a stirring state, replacing with nitrogen until the vacuum degree is more than or equal to-0.095 MPa and the pressure is 0.15-0.25 MPa, heating to 80-130 ℃, vacuumizing for 30-90 min, removing small molecular substances, and heating to 100-150 ℃ to perform a first-stage alkoxylation reaction, wherein the reaction conditions are as follows: continuously and slowly adding (x +2) m moles of alkoxylation reagent at the temperature of 100-200 ℃ and under the pressure of below 0.45MPa, so that the reaction pressure is not more than 0.45MPa, the temperature is stable, after finishing dripping, carrying out a second-stage alkoxylation reaction, wherein the reaction conditions are as follows: continuously and slowly adding (x +2) n moles of an alkoxylating reagent at the temperature of 100-200 ℃ and under the pressure of less than 0.45MPa, keeping the reaction pressure not more than 0.45MPa, stabilizing the temperature, curing for 0.5-4 h at the temperature of 120-180 ℃ until the pressure is constant (namely the pressure is not reduced), then cooling to the temperature of less than 80 ℃, adding a pH value regulator, and stirring to regulate the pH value of the system to 5-8 to obtain the comb-structure nonionic surfactant.
Wherein the alkoxylation agent is ethylene oxide, propylene oxide or butylene oxide.
The catalyst II is one or a mixture of more than two of basic catalyst, acidic catalyst or double metal cyanide complex (DMC).
Wherein the basic catalyst comprises alkali metal (main group I) or alkaline earth metal (main group II), alkali metal or alkaline earth metal alkoxide (such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc.), oxide or hydroxide (such as KOH, NaOH, Mg (OH)2Etc.) and strong basic weak acid salts (such as: sodium carbonate, potassium acetate, calcium acetate), and the like.
The acidic catalyst includes a protonic acid (e.g., sulfuric acid, fluorosulfonic acid, trifluoroacetic acid, etc.) or a Lewis acid (e.g., aluminum trichloride, boron trifluoride etherate, tin tetrachloride, etc.).
The pH regulator is weak acid or weak base, such as acetic acid, phosphoric acid or sodium carbonate.
Example 1
Putting 900g of refined pentadecenyl (alkyl) m-phenol into a reactor, adding 2.7g of p-toluenesulfonic acid, heating to 50-80 ℃, adding 60g of formaldehyde for four times, heating to 80-100 ℃ in a nitrogen atmosphere, carrying out reflux reaction for 2 hours, heating to 100-180 ℃ for reflux reaction for 2 hours, vacuumizing and dehydrating for 2 hours, and removing about 36g of water to obtain pentadecenyl (alkyl) m-phenol oligomer.
Putting 924g of refined pentadecenyl m-phenol oligomer into a high-pressure reactor, adding 5.4g of 50% potassium hydroxide solution, performing nitrogen replacement, and controlling the vacuum degree to be more than or equal to-0.095 MPa and the replacement pressure to be 0.15-0.25 MPa; after nitrogen displacement is finished, heating to 110-130 ℃ for dehydration, after dehydration, heating to 135-160 ℃, adding 174g of propylene oxide for epoxidation reaction, controlling the temperature of addition reaction to 130-190 ℃ and the pressure to be below 0.3MPa, after the addition reaction is finished, adding 1320g of ethylene oxide for epoxidation reaction, controlling the temperature of addition reaction to 130-190 ℃ and the pressure to be below 0.3MPa, after the addition reaction is finished, cooling to 65-75 ℃, and then adding a proper amount of acetic acid for neutralization until the pH value is 5.0-8.0, thereby obtaining the alkoxylated oligopentadiene (alkane) based m-phenol.
Example 2
Putting 600g of refined pentadecenyl m-phenol into a reactor, adding 6g of oxalic acid, heating to 50-80 ℃, adding 30g of formaldehyde for four times, heating to 80-100 ℃ in a nitrogen atmosphere, carrying out reflux reaction for 2 hours, heating to 100-180 ℃ for reflux reaction for 2 hours, vacuumizing and dehydrating for 2 hours to obtain the pentadecenyl m-phenol oligomer.
Putting 612g of refined pentadecenyl m-phenol oligomer into a high-pressure reactor, adding 3.6g of 50% potassium hydroxide solution, performing nitrogen replacement, and controlling the vacuum degree to be more than or equal to-0.095 MPa and the replacement pressure to be 0.15-0.25 MPa; after nitrogen displacement is finished, heating to 110-130 ℃ for dehydration, after dehydration is finished, heating to 135-160 ℃, adding 1320g of ethylene oxide for epoxidation reaction, controlling the temperature of addition reaction to 130-190 ℃ and the pressure to be below 0.3MPa, cooling to 65-75 ℃ after the addition reaction is finished, and then adding a proper amount of acetic acid for neutralization until the pH value is 5.0-8.0, thereby obtaining the alkoxylated oligopentadienyl m (alkyl) resorcinol.
Example 3
Putting 1500g of refined pentadecenyl m-phenol into a reactor, adding 7.5g of oxalic acid and 1.5g of p-toluenesulfonic acid, heating to 50-80 ℃, adding 120g of formaldehyde in four times, heating to 80-100 ℃ in a nitrogen atmosphere, carrying out reflux reaction for 2 hours, heating to 100-180 ℃ for reflux reaction for 2 hours, vacuumizing and dehydrating for 2 hours to obtain the pentadecenyl m-phenol oligomer.
1548g of refined pentadecenyl m-phenol oligomer is put into a high-pressure reactor, 15g of 30% sodium methoxide methanol solution is added for nitrogen replacement, the vacuum degree is controlled to be more than or equal to-0.095 MPa, and the replacement pressure is controlled to be 0.15-0.25 MPa; after nitrogen displacement is finished, heating to 110-130 ℃ for removing small molecules, heating to 135-160 ℃ after the removal of the small molecules is finished, adding 3080g of ethylene oxide for epoxidation, controlling the temperature of addition reaction at 130-190 ℃ and the pressure below 0.3MPa, cooling to 65-75 ℃ after the addition reaction is finished, adding a proper amount of acetic acid for neutralization until the pH value is 5.0-8.0, and obtaining the alkoxylated oligomeric pentadecene (alkyl) m-phenol.
Example 4
Putting 600g of refined pentadecenyl m-phenol into a reactor, heating to 50-80 ℃, adding 60g of formaldehyde and 61g of monoethanolamine in portions, heating to 80-100 ℃ in a nitrogen atmosphere, carrying out reflux reaction for 2 hours, heating to 100-180 ℃ for reflux reaction for 2 hours, vacuumizing and dehydrating for 2 hours to obtain pentadecenyl m-phenol oligomer.
685g of refined pentadecenyl m-phenol oligomer is put into a high-pressure reactor, 6.85g of 30% sodium methoxide methanol solution is added, nitrogen replacement is carried out, the vacuum degree is controlled to be more than or equal to-0.095 MPa, and the replacement pressure is controlled to be 0.15-0.25 MPa; after nitrogen displacement is finished, heating to 110-130 ℃ for removing small molecules, heating to 135-160 ℃ after the removal of the small molecules is finished, adding 1320g of ethylene oxide for epoxidation, controlling the temperature of addition reaction to 130-190 ℃ and the pressure to be below 0.3MPa, cooling to 65-75 ℃ after the addition reaction is finished, adding a proper amount of acetic acid for neutralization until the pH value is 5.0-8.0, and obtaining the alkoxylated oligomeric pentadecene (alkyl) m-phenol.
Example 5
Putting 900g of refined pentadecenyl (alkyl) m-phenol into a reactor, adding 9g of oxalic acid, heating to 50-80 ℃, adding 60g of formaldehyde for four times, heating to 80-100 ℃ in a nitrogen atmosphere, carrying out reflux reaction for 2 hours, heating to 100-180 ℃ for reflux reaction for 2 hours, and carrying out vacuum dehydration for 2 hours to obtain pentadecenyl (alkyl) m-phenol oligomer.
Putting 924g of refined pentadecenyl m-phenol oligomer into a high-pressure reactor, adding 5.5g of 50% potassium hydroxide solution, performing nitrogen replacement, and controlling the vacuum degree to be more than or equal to-0.095 MPa and the replacement pressure to be 0.15-0.25 MPa; after nitrogen displacement is finished, heating to 110-130 ℃ for dehydration, after dehydration, heating to 135-160 ℃, adding 696g of propylene oxide for epoxidation reaction, controlling the temperature of addition reaction to 130-190 ℃ and the pressure to be below 0.3MPa, after the addition reaction is finished, adding 1584g of ethylene oxide for epoxidation reaction, controlling the temperature of addition reaction to 130-190 ℃ and the pressure to be below 0.3MPa, after the addition reaction is finished, cooling to 65-75 ℃, and then adding a proper amount of acetic acid for neutralization until the pH value is 5.0-8.0, thereby obtaining the alkoxylated oligopentadiene (alkane) based m-phenol.
Example 6
Putting 906g of refined pentadecenyl m-phenol into a reactor, adding 9g of oxalic acid, heating to 50-80 ℃, adding 60g of formaldehyde for four times, heating to 80-100 ℃ in a nitrogen atmosphere, carrying out reflux reaction for 2 hours, heating to 100-180 ℃ for reflux reaction for 2 hours, vacuumizing and dehydrating for 2 hours to obtain pentadecenyl m-phenol oligomer.
Putting 924g of refined pentadecyl (en) yl m-phenol oligomer into a high-pressure reactor, adding 5.5g of 50% potassium hydroxide solution, performing nitrogen replacement, and controlling the vacuum degree to be more than or equal to-0.095 MPa and the replacement pressure to be 0.15-0.25 MPa; after nitrogen displacement is finished, heating to 110-130 ℃ for dehydration, after dehydration, heating to 135-160 ℃, adding 1980g of ethylene oxide for epoxidation reaction, controlling the temperature of addition reaction to 130-190 ℃ and the pressure to be below 0.3MPa, after the addition reaction is finished, adding 348g of propylene oxide for epoxidation reaction, controlling the temperature of addition reaction to 130-190 ℃ and the pressure to be below 0.3MPa, after the addition reaction is finished, cooling to 65-75 ℃, and then adding a proper amount of phosphoric acid for neutralization until the pH value is 5.0-8.0, thereby obtaining the alkoxylated pentadecane (alkene) oligomeric meta-phenol.
The appearance and performance parameters of the alkoxylated oligomeric pentadecyl (en) yl-m-phenols obtained in the above examples 1 to 6 are shown in the following table:
Figure BDA0001552144810000111
the comb-structure nonionic surfactant prepared by the embodiment has stable appearance performance, high solid content and moderate viscosity, integrates emulsification and thickening performances, and a dispersion system tends to be stable and fluid; the molecular weight is adjustable, the molecular structure is comb-shaped, the multi-branched structure is also presented, the coating and encapsulation effects on the surface of dispersed particles are good, and the coating has wide application prospects in the industrial fields of aqueous color paste dispersion, emulsification of pesticide raw medicines, papermaking, textile printing and dyeing, wastewater treatment, crude oil extraction and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A preparation method of a nonionic surfactant with a comb-type structure is characterized by comprising the following steps:
(1) synthesizing pentadecenyl meta-phenol or pentadecyl meta-phenol oligomer: adding (x +2) mol of refined pentadecenyl m-phenol or pentadecenyl m-phenol and a catalyst I into a reactor, adding (x +1) mol of a connecting agent in batches at 50-80 ℃, and carrying out reflux reaction in a nitrogen atmosphere to remove small molecular substances to obtain pentadecenyl m-phenol or pentadecenyl m-phenol oligomers; the addition amount of the catalyst I is 0.2-2.0% of the addition amount of the pentadecenyl m-phenol or pentadecenyl m-phenol; the technological conditions of the reflux reaction are as follows: heating to 80-100 ℃ for reflux reaction for 1-3 h, and heating to 100-180 ℃ for reflux reaction for 1-3 h;
(2) synthesis of alkoxylated oligo pentadecyl-or alkoxylated oligo pentadecyl-meta-phenols: adding the pentadecenyl m-phenol or pentadecenyl m-phenol oligomer obtained in the step (1) and a catalyst II into a high-pressure reactor, replacing with nitrogen, removing small molecular substances, and then sequentially adding (x +2) m moles of an alkoxylation reagent and (x +2) n moles of an alkoxylation reagent to perform two-stage alkoxylation; finally, keeping the temperature and curing until the pressure is constant, and adjusting the pH value of the system to be 5-8 to obtain alkoxylated oligo-pentadecenyl m-phenol or alkoxylated oligo-pentadecenyl m-phenol;
the comb-structure nonionic surfactant is alkoxylated pentadecyl-lower m-phenol or alkoxylated pentadecyl-lower m-phenol, and comprises at least one component with the following structural formula:
Figure 611126DEST_PATH_IMAGE001
wherein,
Figure 204306DEST_PATH_IMAGE002
natural cardanol or hydrogenated cardanol; the R is1is-C15H25、-C15H27、-C15H29Or C15H31A linear olefin structure or a linear alkane structure of (a);
the M is a micromolecule connecting group which is connected to the ortho-position or para-position of the phenolic hydroxyl; m is-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(OH)-CH(OH)-、-CH(OH)-CH2-CH(OH)-、-CH(OH)-CH2-CH2-CH2-CH (OH) -、-CH2-NH-CH2-、-CH2-N (CH3) -CH2-、-CH2-N (CH2CH3) -CH2-、-CH2-N(CH2CH2CH3)-CH2-、-CH2-N(CH2CH2OH)-CH2-、-CH2-N(CH3)-N(CH3)-CH2-or-CH2-NH-CH2-CH2-NH-CH2--CH2-NH-CH2-；
P, Q is one or more alkoxy groups which may be the same or different;
x is an integer and is more than or equal to 0 and less than or equal to 30;
m is an integer or a fraction, and m is more than or equal to 0 and less than or equal to 100;
n is an integer or a fraction, and n is more than or equal to 1 and less than or equal to 100.
2. The method for producing a nonionic surfactant having a comb structure according to claim 1, wherein the alkoxy group is-CH2CH2O-、-CH2CH(CH3) O-or-CH2CH(CH2CH3)O-。
3. The method for preparing the nonionic surfactant with the comb-type structure according to claim 1, wherein in the step (2), the addition amount of the catalyst II accounts for 0.03-1.0% of the addition mass of the polymer; the two-stage alkoxylation reaction conditions are as follows: the temperature is 100-200 ℃, the pressure is below 0.45MPa, and the adding speed of the alkoxylating reagent is to keep the reaction pressure not more than 0.45 MPa.
4. The method for preparing the nonionic surfactant with the comb-shaped structure according to claim 1, wherein in the step (2), the temperature for the heat preservation and curing is 120-180 ℃ and the time is 0.5-4 h; the pH value regulator is weak acid or weak base.
5. The method for preparing a nonionic surfactant having a comb-like structure according to claim 1, wherein the catalyst I is a mixture of one or more of acidic or basic compounds; wherein, the acidic compound comprises various inorganic acids, organic acids or other strong acid weak base salt compounds with obvious acidity; the alkaline compound comprises inorganic base, organic base or other strong base weak acid salt compound which shows alkalinity; the catalyst II is one or a mixture of more than two of an alkaline catalyst, an acidic catalyst or a double metal cyanide complex; the alkoxylating agent includes ethylene oxide, propylene oxide or butylene oxide.
6. The method for preparing a nonionic surfactant having a comb structure according to claim 5, wherein in the catalyst I, the inorganic acid comprises hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; the organic acid comprises formic acid, oxalic acid, citric acid, tartaric acid, lactic acid, p-methylsulfonic acid or alkyl benzene sulfonic acid; the inorganic base comprises potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide, magnesium hydroxide or calcium hydroxide; the organic base comprises sodium methoxide, sodium ethoxide, sodium lauryl oxide or sodium isopropoxide; in the catalyst II, the basic catalyst comprises alkali metal in the I main group or alkaline earth metal in the II main group, alkali metal or alkaline earth metal alkoxide, oxide or hydroxide and strong alkali weak acid salt showing alkalinity; the acidic catalyst comprises a protic or lewis acid.
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